WO2007094573A1 - Rigid random coils and composition comprising the same - Google Patents
Rigid random coils and composition comprising the same Download PDFInfo
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- WO2007094573A1 WO2007094573A1 PCT/KR2007/000434 KR2007000434W WO2007094573A1 WO 2007094573 A1 WO2007094573 A1 WO 2007094573A1 KR 2007000434 W KR2007000434 W KR 2007000434W WO 2007094573 A1 WO2007094573 A1 WO 2007094573A1
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- random coil
- random coils
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L101/00—Compositions of unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/44—Carbon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F5/00—Coils
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
- C01P2004/133—Multiwall nanotubes
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2922—Nonlinear [e.g., crimped, coiled, etc.]
- Y10T428/2925—Helical or coiled
Definitions
- the present invention relates to rigid random coils and a composition comprising the same, and more particularly, to rigid random coils, having a contour length larger than the diameter thereof, an average bending ratio D of 0.1-0.8, and a weight average
- the rigid random coils of the present invention having well-defined molecular weight and shape, can be mixed with an organic solvent or a polymer to thus serve as an electrically conductive coating agent, and further, can mitigate problems related to the anisotropy of conventional rod conductive filler, and therefore can be used as a filler or an additive in various organic solvents and polymers.
- a widely known method of imparting electrically non-conductive resin with electrical conductivity uses a resin composition comprising conductive carbon black, carbon fiber, ceramic fiber, or metal fiber. Further, with the aim of reinforcing the strength of the resin, the use of carbon black, carbon fiber, ceramic fiber or metal fiber is preferable. Recently, attempts to realize resin compositions comprising nano- carbon fiber having a diameter of 500 nm or less have been made.
- September 10, 1996) discloses a method of separating and purifying carbon nanotubes depending on the difference in molecular weight, size, and electrical conductivity of the carbon nanotubes.
- Japanese Unexamined Patent Publication No. 2004-244490 (laid open on September 2, 2004) discloses a synthetic resin comprising 0.01 wt% ⁇ l wt% of carbon nanotubes, and also provides a chemical method to increase compatibility between the carbon nanotubes and the resin.
- the carbon nanotube is carbon in a tubular shape, having a diameter ranging from ones to tens of nm, and is classified into a single- walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube, depending on the number of graphene layers. Further, the electrical properties thereof vary in conjunction with the chirality of the graphene. [9] However, carbon is present in many various forms, and the properties thereof vary with the structure thereof. For example, in the case of nanofibers, nano-carbon coils having a helical structure with a diameter of a few nm have been reported (Nano
- an object of the present invention is to provide particles that have a rigid random coil shape, and properties intermediate between those of flexible chain polymers and rigid rod particles, preferably carbon particles having a rigid random coil shape.
- Another object of the present invention is to provide a method of preparing the rigid random coils.
- a further object of the present invention is to provide a resin composition, an organic solution, or an aqueous solution, comprising the rigid random coils.
- the rigid random coils having a contour length larger than the diameter thereof, an average bending ratio D of 0.1-0.8, as represented by Equation 1 below, and a weight average molecular weight of lxl0 8 ⁇ 9xl0 8 g/mole, are provided.
- the present invention provides rigid random coils and a resin composition comprising the same.
- the rigid random coils according to the present invention are mixed with an organic solvent or a polymer and are thus used as an electrically conductive coating agent or plastic, isotropic material can be formed, unlike conventional rod conductive fillers.
- the rigid random coils of the present invention serve as a reinforcing agent for plastics, they can be used as additives or fillers in various organic solvents and polymers because they mitigate problems related to the anisotropy of conventional rod reinforcing filler. In this way, the rigid random coils of the present invention are expected to be efficiently applied to related fields.
- FIG. 1 is a scanning electron micrograph photograph illustrating the rigid random coils obtained in Example 1 of the present invention.
- the rigid random coils having a contour length larger than the diameter thereof, an average bending ratio D b of 0.1-0.8, as represented by the following equation (1): [23]
- R is the end-to-end distance vector
- N is the number of segments
- b is the length of the segment
- Nb is the contour length
- the rigid random coils are characterized in that they have a specific shape and molecular weight and thus have properties intermediate between those of flexible chain polymers and rigid rod particles.
- the rigid random coils of the present invention are bent through permanent deformation, and the distribution of the bending point is well defined. Further, the rigid random coils of the present invention are a new type of particle, unlike helical coils, flexibly bendable fibers, or polymers. In the present invention, a technique for discretely separating and dispersing the rigid random coils of the present invention while greatly mitigating the difference in the properties thereof according to the direction is provided.
- the rigid random coils of the present invention have the properties intermediate between those of the flexible coils and the rigid rod particles. More particularly, the contour length is greater than the diameter thereof, and is preferably 10 times or more. The average bending ratio is less than 1, and is preferably 0.8 or less.
- the contour length is equal to or smaller than the diameter thereof, the rigid random coil of the present invention can not be regarded as being a coil. Therefore, the contour length should be greater than the diameter, and the average bending ratio should be less than 1, in order to realize a bended shape.
- R is the end-to-end distance vector
- r is the distance vector of a monomer
- N is the degree of polymerization of a polymer
- b is the statistically defined monomer length.
- N is the number of segments
- r is the vector of which the length is b and the direction is i
- b is the statistical length of the segment.
- bN is the contour length L.
- D of the rigid random coil is larger than 1/N and is small b er than 1.
- the equation (3) becomes the same as b the equation (2), and thus the rigid random coils have properties similar to those of the flexible coils.
- D b is equal to 1
- the end-to-end distance is the same as the contour length, and thus the rigid random coils have properties corresponding to those of the rigid rod particles.
- the average bending ratio D b may be determined by experimentally measuring the contour length and the end-to-end distance according to the following equation (4): [40]
- R is the end-to-end distance vector
- L is the contour length.
- the equation (4) can be derived from the equation (3).
- the contour length and the end- to-end distance may be measured through SEM, TEM, or AFM, and the average end- to-end distance may be measured through static light scattering.
- the radius of gyration is determined from the pair correlation function, as represented by the equation (5):
- a is the axial length of the rigid rod, which is the same as the end-to-end distance, as defined in the equation (5), and D is, as the flexibility ratio, the persistence length times two divided by the length a.
- the flexibility ratio of the material is determined by the bending modulus, the outer diameter and inner diameter, and the change in the outer diameter and inner diameter in the axial direction. For example, in the case of multi- walled carbon nanotubes having an outer diameter of 18 nm, the flexibility ratio is measured to be about 0.21.
- the radius of gyration may be determined through static light scattering, X-ray scattering, and small angle neutron scattering.
- N avo is the Avogadro number
- V H is the equivalent hydrodynamic volume obtained from the Stokes-Einstein's correlation equation of the diffusion coefficient, which is determined by measuring the translational diffusion coefficient through dynamic light scattering.
- ⁇ the Simha factor
- ⁇ is the ratio of the axial length and the equatorial radius, in which the axial length is identical to the end-to-end distance, the equatorial radius being determined from the above equivalent hydrodynamic volume.
- the Simha factor is disclosed in J. Chem. Phys. VoI 23, 1526-1532 (1955), and may also be calculated from the following equation (8): [50]
- JV - aR. 2 a 2 a n + R, 2 ⁇ 0
- the shape of the rigid random coil of the present invention is defined as the bending ratio of the equation (4).
- the shape and size of the rigid random coils may be determined not only using SEM, TEM or AFM but also using the following hy- drodynamic process.
- the end-to-end distance in Equation 4 may be calculated by sub- stituting the radius of gyration R , measured through static light scattering, into the g equation (5) or (6).
- the equivalent hydrodynamic radius measured through dynamic light scattering the equivalent hydrodynamic radius measured through dynamic light scattering.
- the contour length may be determined through Atomic Simulation (Materials studio v4.0, Accerlrys, USA) using data of the weight average molecular weight, the interlayer spacing of 0.35 nm and the C-C bonding distance of 0.142 nm, obtained through TEM, and the average inner diameter and average outer diameter obtained through TEM. Furthermore, from the ratio between the end-to-end distance and the contour length, determined by the hydrodynamic method, the bending ratio may be determined. Consequently, the molecular weight and the bending ratio of the rigid random coils which are thus determined, coincide with the molecular weight and the bending ratio obtained by co unting the SEM images.
- the material for the rigid random coils of the present invention is not limited as long as it represents the specific shape and dynamic behaviors as mentioned above, and preferably comprises carbon or carbon nanotubes.
- the present invention relates to a method of preparing the rigid random coils.
- the method of preparing the rigid random coils comprises a first step of sonicating a multi-walled carbon nanotube aggregate or carbon fiber, a second step of adding strong acid to the product of the first step and then performing sonication, and a third step of adding a solvent to the product of the second step and performing sonication.
- the first step is a process of sonicating the multi- walled carbon nanotubes or carbon fiber in order to increase reactivity with the strong acid to be added in the second step.
- the multi- walled carbon nanotube is preferably prepared by supporting a metal catalyst on ceramic powder and then performing chemical vapor deposition.
- the ceramic powder is exemplified by aluminum oxides or silicon oxides, and the metal catalyst preferably includes an Fe catalyst.
- the step of sonicating the multi-walled carbon nanotube or carbon fiber be performed at 20-60 W for 40-200 min using an emulsifier-containing aqueous solution or purified water.
- the second step is a process of adding the strong acid to the product of the first step and performing sonication in order to cut and separate the carbon nanotube aggregate and dissolve the ceramic powder.
- the strong acid include, but are not limited to, nitric acid, hydrochloric acid, or sulfuric acid, and sonication is preferably conducted at 20-60 W for 40-200 min.
- the third step is a process of adding the solvent to the product of the second step and performing sonication to realize dispersion in the solvent.
- the solvent include, but are not limited to, tetrahydrofuran (THF), CHCl , or dimethyl- formamide, and sonication is preferably conducted at 20-60 W for 40-200 min.
- the method of preparing the rigid random coils of the present invention preferably further comprises a fourth step of centrifuging the product of the third step to extract a portion, which is uniformly dispersed in the solution.
- the fourth step is a process of separating the rigid random coils from the product of the third step. To this end, centrifugation is performed for 10-60 min, thereby obtaining only the portion dispersed in the solution.
- the present invention relates to a rigid random coil thin film, obtained by filtering the rigid random coils prepared using the above preparation method.
- the random coil thin film may be obtained by filtering the rigid random coils, uniformly dispersed in the solvent or aqueous solution in the third step, using a ceramic or polymer filter having a pore size of 20-200 nm.
- the thickness of the random coil thin film ranges from 30 nm to 10 ⁇ m.
- the shape of the film is maintained using the van der Waals force of the rigid random coils, or alternatively is maintained by applying another polymer thin film.
- the random coil thin film of the present invention may also be used as a gas diffusion layer of the fuel cell. Further, since the random coil thin film is transparent and has electrical conductivity and electromagnetic blocking properties, it is suitable for use as transparent electromagnetic blocking material for touch panels, switches, or displays, such as LCDs or PDPs requiring such properties.
- the present invention relates to a resin composition, an organic solution or an aqueous solution, comprising the rigid random coils.
- the rigid random coils are preferably contained in the resin composition, the organic solution or the aqueous solution in an amount of 0.0001-30 wt%. When the amount is less than 0.0001 wt%, there are no additional effects. On the other hand, if the amount exceeds 30 wt%, the molding process is difficult to perform and the strength may be decreased.
- the resin which may comprise the rigid random coils of the present invention, includes both thermoplastic resin and thermosetting resin.
- the resin include, but are not limited to, one or more selected from the group consisting of polycarbonate, polybutylene terephthalate, polyethylene terephthalate, aromatic polyamide, polyamide, polystyrene, polyphenylenesulfide, thermotropic liquid crystalline polymers, polysulfone, polyetherimide, polyetheretherketone, polyarylate, polymethylmethylacrylate, polyvinylalcohol, polypropylene, polyethylene, polyacry- lonitrile butadiene styrene copolymers, polytetramethyleneoxide-l,4-butanediol copolymers, styrene copolymers, fluorine resins, polyvinyl chloride, polyacrylonitrile, syndiotactic polystyrene, polynorbomene, epoxy resin
- Examples of the organic solvent of the organic solution preferably include dimethylformamide (DMF), toluene, xylene, methylene chloride, n-hexane, dimethyl- sulfoxide, chloroform, tetrahydrofuran (THF), and hydrocarbon organic solvents.
- DMF dimethylformamide
- xylene methylene chloride
- n-hexane dimethyl- sulfoxide
- chloroform tetrahydrofuran
- hydrocarbon organic solvents hydrocarbon organic solvents.
- aqueous solution aqueous solutions containing various emulsifiers are particularly useful.
- the rigid random coils of which the molecular weight and shape are well defined, may be mixed with the organic solvent or polymer and thus used as an electrically conductive coating agent.
- the rigid random coils of the present invention are used as a reinforcing agent for plastics, they can mitigate problems related to the anisotropy of conventional rod reinforcing filler, for example, problems including mechanical strength, electrical/thermal conductivity, linear expansion coefficient, or shrinkage, and therefore can be used as an additive or filler in various organic solvents and polymers.
- the rigid random coils thus prepared were filtered, resulting in a thin film, the surface resistance of which was measured to be 50 Ohm or less.
- Example 1 was mixed with polycarbonate dissolved in THF so that the rigid random coils were contained in an amount of 0.5 wt%, followed by film casting.
- the rigid random coils thus prepared were filtered to thus obtain a thin film 1 ⁇ m thick, the surface resistance of which was measured to be 10 ⁇ Ohm/sq.
- Example 1 The present example was conducted in the same manner as in Example 1, with the exception that carbon fiber, rather than carbon nanotube, was used.
- the resultant rigid random coils had a contour length 20 times the diameter thereof, and a bending ratio of 0.4, corresponding to the properties of rigid random coils.
- the shape of the rigid random coils was not limited only to the tube as in Example 1.
- the surface resistance of the resin composition containing the rigid random coils was measured to be 10 ⁇ Ohm/sq, and the bending strength of the injection-molded test piece in a transverse direction, perpendicular to the mold direction, was determined to be 80-90% of the bending strength of 1200 D/D in the mold direction (ASTM D790). Thereby, the difference in properties according to direction was confirmed to be very small.
- the mold shrinkage (ASTM D955) was 0.5% in a mold direction and 0.6% in a transverse direction, and thus differed by a factor of 1.2 according to the direction, resulting in superior isotropy.
- the surface resistance of the resin composition containing the rigid rod carbon fiber was measured to be 10 ⁇ Ohm/sq, and the bending strength of the injection-molded test piece in a transverse direction perpendicular to the mold direction was determined to be 50-60% of the bending strength of 1300 D/D in the mold direction (ASTM D790). Thereby, the difference in the properties according to the direction was confirmed to be large.
- the mold shrinkage (ASTM D955) was 0.3% in a mold direction and 0.6% in a transverse direction, and thus differed by a factor of 2.0 according to the direction.
- the present invention provides rigid random coils and a resin composition comprising the same.
- the rigid random coils according to the present invention are mixed with an organic solvent and a polymer and are thus used as an electrically conductive coating agent or plastic, isotropic material can be formed, unlike conventional rod conductive fillers.
- the rigid random coils of the present invention serve as a reinforcing agent for plastics, they can be used as additives or fillers in various organic solvents and polymers because they mitigate problems related to the anisotropy of conventional rod reinforcing filler. In this way, the rigid random coils of the present invention are expected to be efficiently applied in related fields.
Abstract
Disclosed are rigid random coils, having a contour length larger than a diameter thereof, an average bending ratio Db of 0.1~0.8, and a weight average molecular weight of 1x108~9x108 g/ mole, and a resin composition or organic solvent composition including the same. The rigid random coils have the properties intermediate between those of polymers and rigid rod particles, and thus may be used as filler of various resins, aqueous solutions or organic solvents.
Description
Description
RIGID RANDOM COILS AND COMPOSITION COMPRISING
THE SAME
Technical Field
[1] The present invention relates to rigid random coils and a composition comprising the same, and more particularly, to rigid random coils, having a contour length larger than the diameter thereof, an average bending ratio D of 0.1-0.8, and a weight average
8 8 b molecular weight of 1x10 -9x10 g/mole, and to a resin composition or organic solvent composition comprising the same.
[2] The rigid random coils of the present invention, having well-defined molecular weight and shape, can be mixed with an organic solvent or a polymer to thus serve as an electrically conductive coating agent, and further, can mitigate problems related to the anisotropy of conventional rod conductive filler, and therefore can be used as a filler or an additive in various organic solvents and polymers.
[3]
Background Art
[4] Generally, a widely known method of imparting electrically non-conductive resin with electrical conductivity uses a resin composition comprising conductive carbon black, carbon fiber, ceramic fiber, or metal fiber. Further, with the aim of reinforcing the strength of the resin, the use of carbon black, carbon fiber, ceramic fiber or metal fiber is preferable. Recently, attempts to realize resin compositions comprising nano- carbon fiber having a diameter of 500 nm or less have been made.
[5] The carbon nanotube was invented in the year 1991 (Nature, 354, 56-58, 1991), and a method of synthesizing large amounts of carbon nanotubes is disclosed in Japanese Unexamined Patent Publication No. 1994-280116 (laid open on October 4, 1994).
[6] Japanese Unexamined Patent Publication No. 1996-231210 (laid-open on
September 10, 1996) discloses a method of separating and purifying carbon nanotubes depending on the difference in molecular weight, size, and electrical conductivity of the carbon nanotubes.
[7] In addition, Japanese Unexamined Patent Publication No. 2004-244490 (laid open on September 2, 2004) discloses a synthetic resin comprising 0.01 wt%~l wt% of carbon nanotubes, and also provides a chemical method to increase compatibility between the carbon nanotubes and the resin.
[8] Typically, the carbon nanotube is carbon in a tubular shape, having a diameter ranging from ones to tens of nm, and is classified into a single- walled carbon nanotube,
a double-walled carbon nanotube, and a multi-walled carbon nanotube, depending on the number of graphene layers. Further, the electrical properties thereof vary in conjunction with the chirality of the graphene. [9] However, carbon is present in many various forms, and the properties thereof vary with the structure thereof. For example, in the case of nanofibers, nano-carbon coils having a helical structure with a diameter of a few nm have been reported (Nano
Letters, 3, 1299-1304, 2003). [10] Thus, conventional carbon nanotubes are thoroughly studied with regard to the size of the diameter thereof. Further, with respect to the shape thereof, exemplary are rigid rods or helices. However, the rigid rod is disadvantageous because it is in a liquid crystal state at a specific concentration and thus undesirably undergoes phase separation, and also the strength thereof changes considerably according to its orientation. [11] Therefore, particles having a bendable shape, that is, a rigid random coil shape, and properties intermediate between those of flexible chain polymers and rigid rod particles, have been considered with the goal of mitigating the above problems.
However, research thereon has not yet been conducted. [12]
Disclosure of Invention
Technical Problem [13] Accordingly, an object of the present invention is to provide particles that have a rigid random coil shape, and properties intermediate between those of flexible chain polymers and rigid rod particles, preferably carbon particles having a rigid random coil shape. [14] Another object of the present invention is to provide a method of preparing the rigid random coils. [15] A further object of the present invention is to provide a resin composition, an organic solution, or an aqueous solution, comprising the rigid random coils. [16]
Technical Solution
[17] According to the present invention, the rigid random coils, having a contour length larger than the diameter thereof, an average bending ratio D of 0.1-0.8, as represented by Equation 1 below, and a weight average molecular weight of lxl08~9xl08 g/mole, are provided. Advantageous Effects
[18] As described hereinbefore, the present invention provides rigid random coils and a resin composition comprising the same. In the case where the rigid random coils
according to the present invention are mixed with an organic solvent or a polymer and are thus used as an electrically conductive coating agent or plastic, isotropic material can be formed, unlike conventional rod conductive fillers. Further, in the case where the rigid random coils of the present invention serve as a reinforcing agent for plastics, they can be used as additives or fillers in various organic solvents and polymers because they mitigate problems related to the anisotropy of conventional rod reinforcing filler. In this way, the rigid random coils of the present invention are expected to be efficiently applied to related fields.
[19]
Brief Description of the Drawings
[20] FIG. 1 is a scanning electron micrograph photograph illustrating the rigid random coils obtained in Example 1 of the present invention.
[21]
Mode for the Invention
[22] According to the present invention, the rigid random coils, having a contour length larger than the diameter thereof, an average bending ratio D b of 0.1-0.8, as represented by the following equation (1): [23]
(i)
[24] wherein R is the end-to-end distance vector, N is the number of segments, b is the length of the segment, and Nb is the contour length,
[25] and a weight average molecular weight of lxl08~9xl08 g/mole, are provided.
[26] When the bending ratio is less than 0.1, it is difficult to show electrical conductivity because the defect rate is high. Further, when the weight average molecular weight is less than 1x10 g/mole, it is difficult to exhibit electrical conductivity and rigidity in the rigid random coils when mixed with the resin. On the other hand, when the bending ratio exceeds 0.8, it is difficult to obtain isotropic material, attributable to excessive anisotropy. Also, when the weight average molecular weight exceeds 9x10 g/mole, particles become entangled with each other, and are thus difficult to uniformly disperse.
[27] In the present invention, the rigid random coils are characterized in that they have a specific shape and molecular weight and thus have properties intermediate between those of flexible chain polymers and rigid rod particles.
[28] That is, the rigid random coils of the present invention are bent through permanent
deformation, and the distribution of the bending point is well defined. Further, the rigid random coils of the present invention are a new type of particle, unlike helical coils, flexibly bendable fibers, or polymers. In the present invention, a technique for discretely separating and dispersing the rigid random coils of the present invention while greatly mitigating the difference in the properties thereof according to the direction is provided.
[29] To this end, the hydrodynamic radius, average diameter, molecular weight, bending ratio, and apparent density of the rigid random coils are statistically defined and analyzed.
[30] The rigid random coils of the present invention have the properties intermediate between those of the flexible coils and the rigid rod particles. More particularly, the contour length is greater than the diameter thereof, and is preferably 10 times or more. The average bending ratio is less than 1, and is preferably 0.8 or less.
[31] As such, if the contour length is equal to or smaller than the diameter thereof, the rigid random coil of the present invention can not be regarded as being a coil. Therefore, the contour length should be greater than the diameter, and the average bending ratio should be less than 1, in order to realize a bended shape.
[32] In the flexible coils, properties exhibited when most of the polymers are in a solution state or a molten state, that is the ensemble average of the end-to-end distance vector to the second power is represented by the following equation (2):
[33]
(2)
[34] wherein R is the end-to-end distance vector, r is the distance vector of a monomer,
N is the degree of polymerization of a polymer, and b is the statistically defined monomer length.
[35] Further, in the group of rigid random coils, the spatial average of the square end- to-end distance vector to the second power is represented by the following equation (3):
[36]
(3)
, φ is the fraction of the segment ( φ, = N1 /N
) in the i direction, N is the number of segments, r is the vector of which the length is b and the direction is i, and b is the statistical length of the segment. Thus, bN is the contour length L. [38] In the above equation (3), D of the rigid random coil is larger than 1/N and is small b er than 1. In the case where D is equal to 1/N, the equation (3) becomes the same as b the equation (2), and thus the rigid random coils have properties similar to those of the flexible coils. On the other hand, in the case where D b is equal to 1, the end-to-end distance is the same as the contour length, and thus the rigid random coils have properties corresponding to those of the rigid rod particles. [39] The average bending ratio D b may be determined by experimentally measuring the contour length and the end-to-end distance according to the following equation (4): [40]
R1
(4)
[41] wherein R is the end-to-end distance vector, and L is the contour length. The equation (4) can be derived from the equation (3). The contour length and the end- to-end distance may be measured through SEM, TEM, or AFM, and the average end- to-end distance may be measured through static light scattering.
[42] Further, the radius of gyration is determined from the pair correlation function, as represented by the equation (5):
[43]
Rg 2 = (R2) /12 = a2 /12
(5) [44] wherein a is the axial length of the rigid rod, which is the same as the end-to-end distance of the rigid random coil. If the rigid random coil is slightly flexible, the radius of gyration R is represented by the following equation (6):
Rs 2 = a2Dc / 6
(6)
[46] wherein a is the axial length of the rigid rod, which is the same as the end-to-end distance, as defined in the equation (5), and D is, as the flexibility ratio, the persistence length times two divided by the length a. The flexibility ratio of the material is determined by the bending modulus, the outer diameter and inner diameter, and the change in the outer diameter and inner diameter in the axial direction. For example, in the case of multi- walled carbon nanotubes having an outer diameter of 18 nm, the flexibility ratio is measured to be about 0.21. The radius of gyration may be determined through static light scattering, X-ray scattering, and small angle neutron scattering.
[47] Further, the intrinsic viscosity of the rigid random coil is represented by the following equation (7):
[48]
[η]= (Nam nmvH !Mw)υ
(7) [49] wherein N avo is the Avogadro number, and V H is the equivalent hydrodynamic volume obtained from the Stokes-Einstein's correlation equation of the diffusion coefficient, which is determined by measuring the translational diffusion coefficient through dynamic light scattering. Further, υ, the Simha factor, is the ratio of the axial length and the equatorial radius, in which the axial length is identical to the end-to-end distance, the equatorial radius being determined from the above equivalent hydrodynamic volume. The Simha factor is disclosed in J. Chem. Phys. VoI 23, 1526-1532 (1955), and may also be calculated from the following equation (8): [50]
υ = (J + K - L) JF sin40sin22ψdΩ + L jfsin2 ΘdΩ. + M JF cos2 ΘdΩ + — JFsin2 θsm2φdΩ
(8)
[51] wherein
[52]
[53]
2Re 2ao
[54]
1 2
L =
[55]
1 1 oR/ Ricco
[56] a1 - Rl
JV = - aR.2 a2an + R,2β0
[57]
[58]
[59]
[60]
^^ hf^l
[61]
[62]
2p2 f 3 (2p2 + l)
[63] i ln P -(P2 -i)1/ 2 (P2 -i)1'2 P + (^ -D1'2
[64] The shape of the rigid random coil of the present invention is defined as the bending ratio of the equation (4). The shape and size of the rigid random coils may be determined not only using SEM, TEM or AFM but also using the following hy- drodynamic process. The end-to-end distance in Equation 4 may be calculated by sub-
stituting the radius of gyration R , measured through static light scattering, into the g equation (5) or (6). In addition, using the equivalent hydrodynamic radius measured through dynamic light scattering, the equatorial volume (
) of the prolate ellipsoid is determined, and thus the equatorial radius (R ) is calculated. e
Further, using the calculated equatorial radius and the axial length a of the equation (5), the axial ratio ( a
) is calculated, from which the Simha factor is determined. The intrinsic viscosity of the rigid random coil is measured, and the weight average molecular weight is determined from the equation (7) using the calculated Simha factor. The contour length may be determined through Atomic Simulation (Materials studio v4.0, Accerlrys, USA) using data of the weight average molecular weight, the interlayer spacing of 0.35 nm and the C-C bonding distance of 0.142 nm, obtained through TEM, and the average inner diameter and average outer diameter obtained through TEM. Furthermore, from the ratio between the end-to-end distance and the contour length, determined by the hydrodynamic method, the bending ratio may be determined. Consequently, the molecular weight and the bending ratio of the rigid random coils which are thus determined, coincide with the molecular weight and the bending ratio obtained by co unting the SEM images.
[65] The material for the rigid random coils of the present invention is not limited as long as it represents the specific shape and dynamic behaviors as mentioned above, and preferably comprises carbon or carbon nanotubes.
[66] In addition, the present invention relates to a method of preparing the rigid random coils.
[67] The method of preparing the rigid random coils comprises a first step of sonicating a multi-walled carbon nanotube aggregate or carbon fiber, a second step of adding strong acid to the product of the first step and then performing sonication, and a third step of adding a solvent to the product of the second step and performing sonication.
[68] The first step is a process of sonicating the multi- walled carbon nanotubes or carbon fiber in order to increase reactivity with the strong acid to be added in the second step. The multi- walled carbon nanotube is preferably prepared by supporting a metal catalyst on ceramic powder and then performing chemical vapor deposition. The ceramic powder is exemplified by aluminum oxides or silicon oxides, and the metal catalyst preferably includes an Fe catalyst. Thus, it is preferred that the step of sonicating the multi-walled carbon nanotube or carbon fiber be performed at 20-60 W
for 40-200 min using an emulsifier-containing aqueous solution or purified water.
[69] The second step is a process of adding the strong acid to the product of the first step and performing sonication in order to cut and separate the carbon nanotube aggregate and dissolve the ceramic powder. Examples of the strong acid include, but are not limited to, nitric acid, hydrochloric acid, or sulfuric acid, and sonication is preferably conducted at 20-60 W for 40-200 min.
[70] The third step is a process of adding the solvent to the product of the second step and performing sonication to realize dispersion in the solvent. Preferably, examples of the solvent include, but are not limited to, tetrahydrofuran (THF), CHCl , or dimethyl- formamide, and sonication is preferably conducted at 20-60 W for 40-200 min.
[71] Also, the method of preparing the rigid random coils of the present invention preferably further comprises a fourth step of centrifuging the product of the third step to extract a portion, which is uniformly dispersed in the solution. The fourth step is a process of separating the rigid random coils from the product of the third step. To this end, centrifugation is performed for 10-60 min, thereby obtaining only the portion dispersed in the solution.
[72] In addition, the present invention relates to a rigid random coil thin film, obtained by filtering the rigid random coils prepared using the above preparation method.
[73] The random coil thin film may be obtained by filtering the rigid random coils, uniformly dispersed in the solvent or aqueous solution in the third step, using a ceramic or polymer filter having a pore size of 20-200 nm. The thickness of the random coil thin film ranges from 30 nm to 10 μm. The shape of the film is maintained using the van der Waals force of the rigid random coils, or alternatively is maintained by applying another polymer thin film. The random coil thin film of the present invention may also be used as a gas diffusion layer of the fuel cell. Further, since the random coil thin film is transparent and has electrical conductivity and electromagnetic blocking properties, it is suitable for use as transparent electromagnetic blocking material for touch panels, switches, or displays, such as LCDs or PDPs requiring such properties.
[74] In addition, the present invention relates to a resin composition, an organic solution or an aqueous solution, comprising the rigid random coils.
[75] The rigid random coils are preferably contained in the resin composition, the organic solution or the aqueous solution in an amount of 0.0001-30 wt%. When the amount is less than 0.0001 wt%, there are no additional effects. On the other hand, if the amount exceeds 30 wt%, the molding process is difficult to perform and the strength may be decreased.
[76] The resin, which may comprise the rigid random coils of the present invention, includes both thermoplastic resin and thermosetting resin. Preferably, examples of the
resin include, but are not limited to, one or more selected from the group consisting of polycarbonate, polybutylene terephthalate, polyethylene terephthalate, aromatic polyamide, polyamide, polystyrene, polyphenylenesulfide, thermotropic liquid crystalline polymers, polysulfone, polyetherimide, polyetheretherketone, polyarylate, polymethylmethylacrylate, polyvinylalcohol, polypropylene, polyethylene, polyacry- lonitrile butadiene styrene copolymers, polytetramethyleneoxide-l,4-butanediol copolymers, styrene copolymers, fluorine resins, polyvinyl chloride, polyacrylonitrile, syndiotactic polystyrene, polynorbomene, epoxy resin, and phenol resin.
[77] Examples of the organic solvent of the organic solution preferably include dimethylformamide (DMF), toluene, xylene, methylene chloride, n-hexane, dimethyl- sulfoxide, chloroform, tetrahydrofuran (THF), and hydrocarbon organic solvents. As the aqueous solution, aqueous solutions containing various emulsifiers are particularly useful.
[78] According to the present invention, the rigid random coils, of which the molecular weight and shape are well defined, may be mixed with the organic solvent or polymer and thus used as an electrically conductive coating agent.
[79] Further, in the case where the rigid random coils of the present invention are used as a reinforcing agent for plastics, they can mitigate problems related to the anisotropy of conventional rod reinforcing filler, for example, problems including mechanical strength, electrical/thermal conductivity, linear expansion coefficient, or shrinkage, and therefore can be used as an additive or filler in various organic solvents and polymers.
[80]
[81] A better understanding of the present invention may be obtained through the following examples and comparative examples, which are set forth to illustrate, but are not to be construed as the limit of the present invention.
[82]
[83] [Example 1] (Preparation of Rigid Random Coils and Thin Film)
[84] 5 g of a multi-walled carbon nanotube aggregate (available from JEIO Co., Ltd.), obtained by supporting a metal (Fe) catalyst on ceramic powder (aluminum oxide) and then performing chemical vapor deposition, was added to 100 g of purified water, and then sonication was conducted at 40 W for 180 min. 50 g of 60% strong nitric acid was added thereto, and then sonication was performed at 40 W for 60 min, so that the aggregate was cut and separated and the ceramic powder was dissolved. Subsequently, the product was washed with purified water, added to 100 g of dimethylformamide, and then subjected to sonication at 40 W for 180 min. The sonicated solution was centrifuged, thus obtaining rigid random coils in the uniform solution, the bending ratio and the weight average molecular weight of which were measured to be 0.32 and
3.43x10 g/mole, respectively. The rigid random coils thus prepared were filtered,
resulting in a thin film, the surface resistance of which was measured to be 50 Ohm or less.
[85]
[86] [Example 2]
[87] A uniform solution of dimethylformamide and rigid random coils, obtained as in
Example 1, was mixed with polycarbonate dissolved in THF so that the rigid random coils were contained in an amount of 0.5 wt%, followed by film casting. The rigid random coils thus prepared were filtered to thus obtain a thin film 1 μm thick, the surface resistance of which was measured to be 10 ~ Ohm/sq.
[88]
[89] [Example 3] (Carbon Fiber Rigid Random Coils)
[90] The present example was conducted in the same manner as in Example 1, with the exception that carbon fiber, rather than carbon nanotube, was used. Thus, the resultant rigid random coils had a contour length 20 times the diameter thereof, and a bending ratio of 0.4, corresponding to the properties of rigid random coils. The shape of the rigid random coils was not limited only to the tube as in Example 1.
[91]
[92] [Example 4] (Preparation of Resin Composition containing Rigid Random Coils)
[93] 481.3 g of polycarbonate, as a thermoplastic resin, 15 g of the rigid random coils prepared in Example 1, 0.2 g of an antioxidant, 2.5 g of a lubricant, and 15 g of a phosphate-based flame retardant were loaded into a twin-screw extruder and mixed at 260°C, thus preparing a resin composition containing rigid random coils.
[94] The surface resistance of the resin composition containing the rigid random coils was measured to be 10 ~ Ohm/sq, and the bending strength of the injection-molded test piece in a transverse direction, perpendicular to the mold direction, was determined to be 80-90% of the bending strength of 1200 D/D in the mold direction (ASTM D790). Thereby, the difference in properties according to direction was confirmed to be very small. The mold shrinkage (ASTM D955) was 0.5% in a mold direction and 0.6% in a transverse direction, and thus differed by a factor of 1.2 according to the direction, resulting in superior isotropy.
[95]
[96] [Comparative Example 1]
[97] A uniform solution of dimethylformamide was prepared as in Example 1, with the exception that 5 g of rigid rod carbon nanotubes were used. The viscosity depending on the concentration was measured using an Ubbe-Lodde viscometer having a diameter of 0.36 mm.
[98] The resultant product of Comparative Example 1 had a contour length of 3000 nm and an intrinsic viscosity of 14, and thus was confirmed to be a typical rod carbon
nanotube without permanent deformation.
[99]
[100] [Comparative Example 2]
[101] 481.3 g of polycarbonate, as a thermoplastic resin, 15 g of rigid rod carbon fiber,
0.2 g of an antioxidant, 2.5 g of a lubricant, and 15 g of a phosphate-based flame retardant were loaded into a twin-screw extruder and mixed at 260°C, thus preparing a resin composition containing the rigid rod carbon fiber.
[102] The surface resistance of the resin composition containing the rigid rod carbon fiber was measured to be 10 ~ Ohm/sq, and the bending strength of the injection-molded test piece in a transverse direction perpendicular to the mold direction was determined to be 50-60% of the bending strength of 1300 D/D in the mold direction (ASTM D790). Thereby, the difference in the properties according to the direction was confirmed to be large. The mold shrinkage (ASTM D955) was 0.3% in a mold direction and 0.6% in a transverse direction, and thus differed by a factor of 2.0 according to the direction.
[103]
Industrial Applicability
[104] As described hereinbefore, the present invention provides rigid random coils and a resin composition comprising the same. In the case where the rigid random coils according to the present invention are mixed with an organic solvent and a polymer and are thus used as an electrically conductive coating agent or plastic, isotropic material can be formed, unlike conventional rod conductive fillers. Further, in the case where the rigid random coils of the present invention serve as a reinforcing agent for plastics, they can be used as additives or fillers in various organic solvents and polymers because they mitigate problems related to the anisotropy of conventional rod reinforcing filler. In this way, the rigid random coils of the present invention are expected to be efficiently applied in related fields.
[105] Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.
[106]
Claims
Claims
[ 1 ] A rigid random coil, having an average bending ratio D of 0.1 -0.8, as b represented by the following equation (4):
R1 '
Db =
U
(4) wherein R is an end-to-end distance vector, and L is a contour length, and a weight average molecular weight of 1x10 -9x10 g/mole. [2] The rigid random coil of claim 1, wherein the contour length is 10 times or more greater than a diameter thereof. [3] The rigid random coil of claim 1 or 2, which is formed by using carbon or carbon nanotube. [4] A method of preparing a rigid random coil, comprising: a first step of sonicating a multi-walled carbon nanotube aggregate or carbon fiber; a second step of adding a strong acid to a product of the first step and performing sonication; and a third step of adding a solvent to a product of the second step and performing sonication. [5] The method of claim 4, wherein the sonication in the first step to the third step is conducted at 20-60 W for 40-200 min. [6] The method of claim 4, wherein the strong acid is nitric acid, hydrochloric acid, or sulfuric acid. [7] The method of claim 4, wherein the solvent is tetrahydrofuran (THF), CHCl , or dimethylformamide. [8] The method of claim 4, further comprising a fourth step of centrifuging a product of the third step. [9] A rigid random coil thin film, obtained by filtering a rigid random coil prepared by using the method of claim 4. [10] A resin composition, comprising 0.0001-30 wt% of the rigid random coil of any one of claims 1 to 3. [11] The resin composition of claim 10, wherein the resin is one or more selected from the group consisting of polycarbonate, polybutylene terephthalate, polyethylene terephthalate, aromatic polyamide, polyamide, polystyrene, polyphenylenesulfide, thermotropic liquid crystalline polymers, polysulfone, polyetherimide, polyetheretherketone, polyarylate, polymethylmethylacrylate,
polyvinylalcohol, polypropylene, polyethylene, polyacrylonitrile butadiene styrene copolymers, polytetramethyleneoxide-l,4-butanediol copolymers, styrene copolymers, fluorine resins, polyvinyl chloride, polyacrylonitrile, syn- diotactic polystyrene, polynorbomene, epoxy resin, and phenol resin.
[12] An organic solution, comprising 0.0001-30 wt% of the rigid random coil of any one of claims 1 to 3.
[13] The organic solution of claim 12, wherein a solvent of the organic solution comprises one or more selected from the group consisting of dimethylformamide (DMF), toluene, xylene, methylene chloride, n-hexane, dimethylsulfoxide, chloroform, tetrahydrofuran (THF), and hydrocarbon organic solvents.
[14] An aqueous solution, comprising 0.0001-30 wt% of the rigid random coil of any one of claims 1 to 3.
[15] The aqueous solution of claim 14, which further comprises an emulsifier.
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KR100900658B1 (en) | 2007-12-18 | 2009-06-01 | 주식회사 엘지화학 | Injection molded electrical-conductive plastic part and electrical-conductive resin composition |
KR100829513B1 (en) * | 2007-12-31 | 2008-05-16 | 한양대학교 산학협력단 | Carbon nanotube reinforced thermotropic liquid crystal polymer nanocomposite and preparation method thereof |
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US8357858B2 (en) * | 2008-11-12 | 2013-01-22 | Simon Fraser University | Electrically conductive, thermosetting elastomeric material and uses therefor |
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KR102065651B1 (en) * | 2015-11-09 | 2020-01-13 | 주식회사 엘지화학 | Carbon composite material having improved permittivity and method for controlling dielectric constant therof |
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RU2644893C1 (en) * | 2016-12-29 | 2018-02-14 | Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" | Method of separation of the product of carbon nanotubes from carbon-catalyst composite |
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EP1984431A1 (en) | 2008-10-29 |
JP2009526733A (en) | 2009-07-23 |
KR100784993B1 (en) | 2007-12-11 |
KR20070082013A (en) | 2007-08-20 |
CN101384647B (en) | 2012-05-30 |
TW200744949A (en) | 2007-12-16 |
TWI344447B (en) | 2011-07-01 |
US8236269B2 (en) | 2012-08-07 |
JP5253181B2 (en) | 2013-07-31 |
EP1984431A4 (en) | 2010-11-03 |
EP1984431B1 (en) | 2012-12-05 |
CN101384647A (en) | 2009-03-11 |
US20080004396A1 (en) | 2008-01-03 |
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